柔性可弯曲高容量复合织物电极的制备及性能

杨超; 夏兆鹏; 王思雨; 李婷; 王亮; 刘雍

doi:10.13801/j.cnki.fhclxb.20211008.002

柔性可弯曲高容量复合织物电极的制备及性能

doi: 10.13801/j.cnki.fhclxb.20211008.002

天津工业大学　纺织科学与工程学院，天津 300387

基金项目: 国家市场监督管理总局科技计划项目(2019MK002)

详细信息

通讯作者:
夏兆鹏，博士，高级工程师，博士生导师，研究方向为天然纤维高值化应用及智能纺织品关键器件研究　E-mail: xia_zhaopeng@163.com

中图分类号: TB333
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出版历程
- 收稿日期: 2021-08-02
- 修回日期: 2021-09-06
- 录用日期: 2021-09-24
- 网络出版日期: 2021-10-09
- 刊出日期: 2022-08-31

Preparation and properties of flexible high capacity composite fabric electrode

School of Textile Science and Engineering, Tiangong University, Tianjin 300387, China

摘要

摘要: 随着科学技术的飞速发展，各种可穿戴智能电子设备随之兴起。这些电子设备对化学电源的性能提出了更高要求，如安全高效且柔性的电化学储能装置。目前，大量的研究致力于柔性储能器件，以满足各种可穿戴智能电子设备供能的需求。本文通过调控甲醇相法的沉积时间，将具有高比表面、高孔隙率的钴基金属有机框架(Co-MOF)和镍钴双氢氧化物(NiCo DH)巧妙地结合在镀镍织物(NF)上，制备出了高性能的柔性复合电极。该电极具有高比容量(22.6 μA·h·cm⁻²(323 mA·h·g⁻¹))、优异的循环性能(2 000次充放电后容量保持率为56%)及良好的倍率性能(电流增大50倍容量保持率为60%)，并且该电极拥有优异的柔韧性，经过多次弯折，该电极的电性能几乎没有大的变化，能够满足服装的各类变形。因此，本文为可穿戴电子设备的能源供应提高了一条新的思路，在智能可穿戴领域有着广阔的前景。
- 复合织物电极 /
- 高容量 /
- 柔性 /
- 金属有机框架 /
- 可穿戴 /
- 镍锌电池
Abstract: With the rapid development of science and technology, a variety of wearable intelligent electronic devices rised. These electronic devices put forward higher requirements for the performance of chemical power supply, such as safe, efficient and flexible electrochemical energy storage devices. At present, a lot of research was devoted to flexible energy storage devices to meet the energy supply needs of various wearable intelligent electro-nic devices. By adjusting the deposition time of methanol phase method, cobalt based metal organic framework (Co-MOF) and nickel cobalt double hydroxide (NiCo DH) with high specific surface and high porosity were cleverly combined on nickel fabric (NF) to prepare high-performance flexible composite electrode. The electrode has a high specific capacity of 22.6 μA·h·cm⁻²(323 mA·h·g⁻¹), excellent cycle performance (the capacity retention rate is 56% after 2000 times of charge and discharge) and good rate performance (the current increases by 50 times, and the capacity retention rate is 60%), and the electrode has excellent flexibility. After many bends, the electrical perfor-mance of the electrode almost does not change greatly, which can meet all kinds of deformation of clothing. Therefore, this research improves a new idea for the energy supply of wearable electronic devices, and has broad prospects in the field of intelligent wearable.
- composite fabric electrode /
- high capacity /
- flexibility /
- metal-organic framework /
- wearable /
- nickel zinc battery

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图 1 镀镍织物-镍钴双氢氧化物(NF-NiCo DH)复合电极材料的制备流程图

Figure 1. Preparation flow chart of nickel plated fabric-NiCo double hydroxides (NF-NiCo DH) composite electrode material

2-MIM—2-Methylimidazole

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图 2 不同沉积时间的NF-金属有机框架(MOF)织物的SEM图像(小图为对应的局部放大图)

Figure 2. SEM images of NF-metal organic framework (MOF) fabric with different deposition time (Small picture is the corresponding local enlarged view)

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图 3 MOF边长和附着量随沉积时间的变化曲线

Figure 3. Variation curve of MOF side length and adhesion with deposition time

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图 4 NF-NiCo DH电极刻蚀前后的SEM图像：((a), (b)) 刻蚀前的NF-MOF；((c), (d)) 刻蚀后的NF-MOF

Figure 4. SEM images of the NF-NiCo DH electrode before and after etching: ((a), (b)) NF-MOF before etching; ((c), (d)) NF-MOF after etching

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图 5 NF-NiCo DH复合电极的XPS全图谱 (a) 和高分辨XPS图谱：(b) Co2p; (c) Ni2p; (d) O1s

Figure 5. XPS full spectrum of NF-NiCo DH composite electrode (a) and high resolution XPS spectra: (b) Co2p; (c) Ni2p; (d) O1s

Sat.—Satellite peak

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图 6 NF和NF-MOF 24电极的BET测试

Figure 6. BET test of NF and NF-MOF 24 electrode

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图 7 不同沉积时间的NF-NiCo DH电极的循环伏安(CV)曲线

Figure 7. Cyclic voltammetry (CV) curves of NF-NiCo DH electrode at different deposition times

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图 8 不同沉积时间的NF-NiCo DH电极在不同电流密度下的容量变化

Figure 8. Capacity changes of NF-NiCo DH electrode at different deposition times under different current densities

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图 9 NF-NiCo DH 24电极在不同扫描速率下的CV曲线

Figure 9. CV curves of NF-NiCo DH 24 electrode at different scanning speeds

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图 10 NF-NiCo DH 24 电极的峰值电流密度与扫描速率的对数关系图

Figure 10. Logarithmic relationship between peak current density and scanning rate of NF-NiCo DH 24 electrode

b—Slope of line

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图 11 NF-NiCo DH 24电极在不同倍率下的放电比容量及效率图

Figure 11. Discharge specific capacity and efficiency of NF-NiCo DH 24 electrode at different magnification

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图 12 NF-NiCo DH 24电极在10 mA·cm⁻²电流密度下的充放电长循环测试图

Figure 12. Charge discharge long cycle test diagram of NF-NiCo DH 24 electrode under 10 mA·cm⁻² current density

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图 13 NF-NiCo DH 24电极弯折前后的容量保持率

Figure 13. Capacity retention rate of NF-NiCo DH 24 electrode before and after bending

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图 14 NF-NiCo DH 24电极弯折400次后的长循环测试图

Figure 14. Long cycle test diagram of NF-NiCo DH 24 electrode after bending 400 times

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图 15 NF-NiCo DH 24电极在镍锌电池中的供能测试

Figure 15. Energy supply test of NF-NiCo DH 24 electrode in nickel zinc battery

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表 1 不同条件下的复合电极材料

Table 1. Composite electrode materials under different conditions

Material	Deposition material	Deposition time/h	Name	Etching	Name
Ni fabric	Co-metal organic framework	6	NF-MOF 6	Nickel cobalt double hydroxide	NF-NiCo DH 6
		12	NF-MOF 12		NF-NiCo DH 12
		18	NF-MOF 18		NF-NiCo DH 18
		24	NF-MOF 24		NF-NiCo DH 24
		30	NF-MOF 30		NF-NiCo DH 30

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表 2 NF-NiCo DH 24电极同其他复合电极材料的电化学比容量对比

Table 2. Comparison of electrochemical specific capacity between NF-NiCo DH 24 electrode and other composite electrode materials

Electrode material	Capacity/ (mA·h·g⁻¹)	Ref.
Co₃O₄@carbon cloth	240.8	[32]
Co₃O₄@carbon cloth	230.0	[33]
Silver-coated nylon fiber@Ni@nickel-cobalt layered double hydroxides	275.0	[30]
NiSe₂@Ni foam	243.8	[34]
Ni₂P@carbon cloth	242.0	[35]
Ni-NiO/carbon cloth	184.0	[36]
Ni fabric-nickel cobalt double hydroxide	323.0	This work

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